Patent GB-864791-A (GB)
Title: Improvements in polyamines
IPC: D06P1/607
Filed: 1957-07-29
Abstract: Soluble, linear polytertiary amines are prepared by reacting, in the presence of an acid acceptor, approximately equimolar proportions of an aliphatic primary monoamine and a polyalkoxy diester of the general formula:-  X(CH2 CH2 O)n CH2 CH2 X or a derivative thereof, wherein X is the esterforming residue of an inorganic acid or an organically substituted sulphuric, phosphoric or sulphonic acid and n is an average number between 1 and 100. The soluble products, or similar soluble products prepared with excess alkylating diester and incomplete reaction, or prepared with excess amine and being of lower molecular weight, may be converted into insoluble cross-linked amine polymers by further reaction with additional alkylating diester which may be the same as or different from the one used initially.  The products contain quaternary ammonium groups.  Suitable amines are methyl, ethyl, propyl, butyl, amyl, hexyl, dodecyl, allyl monoethanol, 3-isopropyl-n-propyl, and 3-methoxy-n-propyl amine. Suitable alkylating diesters are the dichlorides and diiodides of triethylene glycol or of higher polyethylene glycols; polyethylene glycol di-p-toluene sulphonates or dimethane sulphonates. Derivatives thereof are represented by the formula:- X CH2 CH2 (OCH2 CH2)m ORO(CH2 CH2O)n CH2 CH2 X, where m and n are average numbers between 3 and 40 and R is a glycol residue.  Suitable acid acceptors are sodium carbonate, sodium or potassium hydroxide.  The alkylating diesters are prepared from the polyethylene glycols or derivatives by suitable esterification reactions, e.g. with thionyl chloride, sulphamic acid, ptoluene sulphonyl chloride or methane sulphonyl chloride, or by ester-interchange reactions.  Reaction may be in presence of solvents, e.g. water, ethylene glycol, or isopropyl alcohol.  In Examples (1) to (4) and (10) methylamine is reacted in presence of ethylene glycol and sodium carbonate with the dichlorides of various polyethylene glycols.  (5) the amine used was monoethanolamine (6) allylamine was used (7) dodecylamine was used and potassium hydroxide as acid acceptor (8) n-hexyl-amine was used (9) ethylamine was used.  The soluble products are useful for impregnating textiles, being insolubilized in the fibres by reaction with further alkylating diesters (see Group IV(c)).  The insoluble products have ion-exchange properties and may be formed in the presence of inert carrier materials such as silica, gel or other refractories.ALSO:Soluble, linear polytertiary amines are prepared by reacting, in the presence of an acid acceptor, approximately equimolar proportions of an aliphatic primary monoamine (the hydrocarbon chain of which may be interrupted by hereto atoms such as O, N or S) and a polyalkoxy diester of the general formula: X(CH2CH2O)nCH2X or a derivative thereof, wherein X is the ester-forming residue of an inorganic acid or an organically substituted sulphuric, phosphoric or sulphonic acid and n is an average number between 1 and 100.  The soluble products, or similar soluble products prepared with excess alkylating diester and incomplete reaction, or prepared with excess amine and being of lower molecular weight, may be converted into insoluble cross-linked amine polymers by further reaction with additional alkylating diester which may be the same as or different from the one used initially.  The products contain quaternary ammonium groups.  Suitable amines are methyl, ethyl, propyl, butyl, amyl, hexyl, dodecyl, allyl, monoethanol, 3-isopropyl-n-propyl and 3-methoxy-n-propyl amine. Suitable alkylating diesters are the dichlorides and diiodides of triethylene glycol or of higher polyethylene glycols; polyethylene glycol di-p-toluene sulphonates or dimethane sulphonates. Derivatives thereof are represented by the formula: <FORM:0864791/IV (b)/1> , where m and n are average numbers between 3 and 40 and R is a glycol residue.  Suitable acid acceptors are sodium carbonate, sodium or potassium hydroxide.  The alkylating diesters are prepared from the polyethylene glycols or derivatives by suitable esterification reactions, e.g. with thionyl chloride, sulphamic acid, p-toluene sulphonyl chloride or methane sulphonyl chloride, or by ester-interchange reactions.  Reaction may be in presence of solvents, e.g. water, ethylene glycol or isopropyl alcohol.  In Examples (1) to (4) and (10) methylamine is reacted in presence of ethylene glycol and sodium carbonate with the dichlorides of various polyethylene glycols. (5) the amine used was monoethanolamine, (6) allylamine was used, (7) dodecylamine was used and potassium hydroxide as acid acceptor, (8) n-hexyl-amine was used, (9) ethylamine was used.  The soluble products are useful for impregnating textiles, being insolublized in the fibres by reaction with further alkylating diesters (see Group IV(c)).  The insoluble products have ion-exchange properties and may be formed in the presence of inert carrier materials such as silica gel or other refractories.ALSO:Textiles are given improved dyeing and antistatic properties by treating them with water-soluble polymers of primary alkyl amines and diesters of polyalkylene glycols (see Group IV(a) ) and insolubilizing the polymers on the fibres by reaction with further quantities of alkylating diester, which may be the same as or different from the one initially used.  In Examples (11) and (14) an undyed Dacron polyester woven yarn fabric is impregnated in a three roll mill with an aqueous solution of the polymer obtained by reacting together the dichloride of polyethylene glycol and methylamine in presence of ethylene glycol and soda ash and with polyethylene glycol di-iodide in water.  The dried fabric is cured in an oven heated to 150 DEG C. for 3 minutes; (12) Nylon taffeta fabric is similarly treated; (13) Dacron taffeta fabric is impregnated with an aqueous solution containing polyethylene glycol di-iodide and a polyamine obtained from ethylamine and polyethylene glycol dichloride, dried and heated to cure the resin; (15) A dyed Orlon fabric is similarly treated to produce an anti-static finish.